CN111185199A - Z-type heterojunction photocatalyst and preparation method and application thereof - Google Patents
Z-type heterojunction photocatalyst and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/39—
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- B01J35/40—
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- B01J35/50—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a Z-type heterojunction photocatalyst and a preparation method thereof, and Cd is prepared by reacting Cd with Cd2+、Co2+Mixing the obtained product with an organic ligand, and carrying out hydrothermal reaction to obtain Cd/Co-MOF; and then mixing the Cd/Co-MOF with a vulcanizing agent, and carrying out a vulcanization reaction to obtain the Z-type heterojunction photocatalyst. The Z-type heterojunction photocatalyst prepared by the invention can be used in a pure water systemIn the method, hydrogen and benzaldehyde are produced by catalysis, and the yield of hydrogen produced by photocatalysis can reach 61924 mu mol g within 6h‑1The selectivity of benzaldehyde is 99.9%, and the selectivity of benzyl alcohol can reach 72% within 20h, and the benzyl alcohol is used for replacing a sacrificial agent to prepare a high value-added chemical product, so that the cost is effectively reduced, and the application prospect is good.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a Z-type heterojunction photocatalyst as well as a preparation method and application thereof.
Background
H2As a sustainable clean energy carrier, the energy carrier has great potential in solving the problems of energy and environmental crisis and the like, and is receiving attention. Over the past decades, photocatalytic decomposition of water using semiconductors to produce H2Is considered to be an ideal method for converting solar energy into chemical energy. Upon illumination, the semiconductor may generate equal amounts of photogenerated electrons and holes, where the photogenerated electrons are capable of driving the reduction of protons to H2. However, the photogenerated holes will generally recombine with the photogenerated electrons causing photo-corrosion of the photocatalyst, thereby reducing H2The release rate of (c). To achieve high efficiency of H2The generation of H often requires the addition of a sacrificial agent to consume the photogenerated holes, which not only results in the inefficient use of light energy and waste of resources, but also results in the generation of H2Is generally much less valuable than the sacrificial agent. If industrial chemicals with high added value can be formed in the photocatalysis process, the sacrificial agent is replaced to promote H2Will be expected to solve the problem.
Inspired by natural photosynthesis, scientists design various all-solid-state artificial Z-shaped heterojunction photocatalytic systems based on the characteristic that two semiconductors have well-matched energy band structures after being combined. The Z-type heterojunction has a special electron transfer path, can generate photo-generated electrons and holes with enough energy levels under illumination, has a wider light absorption range, and improves the space separation capability of charge carriers.
MOFs are materials composed of organic ligands and metal nodes, and can be used for uniformly dispersing mixed metal centers to form a multi-metal solid solution. In the process of dispersing the metal center, a small-size heterojunction can be formed; meanwhile, the nano particles formed in situ in the multi-metal solid solution are closely connected and can also be formedForming a heterojunction. By adjusting the concentration of the doping metal in the solid solution, the chemical composition and band gap of the heterostructure can be finely adjusted, and thus the light absorption capacity and redox activity can be further optimized. At present, research reports of MOFs for constructing heterojunction are reported, but the existing MOFs-based heterojunction has low photooxidation capability and can be used for photocatalytic H precipitation2A large amount of sacrificial agent is still required to consume the photogenerated holes in the process.
Disclosure of Invention
The present invention is directed to solving one of the technical problems of the prior art, and provides a Z-type heterojunction photocatalyst capable of photocatalytically decomposing water into H without an electron sacrificial agent, and a method for preparing the same2And simultaneously generates high value-added chemicals.
The Z-type heterojunction photocatalyst is prepared by a preparation method comprising the following steps:
(1) adding Cd into the solution2+、Co2+Mixing the obtained product with an organic ligand, and carrying out hydrothermal reaction to obtain Cd/Co-MOF;
(2) and mixing the Cd/Co-MOF with a vulcanizing agent, and carrying out a vulcanization reaction to obtain the Z-type heterojunction photocatalyst.
Further, the hydrothermal reaction temperature is 120-140 ℃, and preferably 130 ℃.
Further, the organic ligand is selected from 5- (5-carboxyl-3-pyridyl) -1, 3-phthalic acid.
Further, the Cd2+、Co2+And organic ligand in a molar ratio of 2: 4: (1-2), preferably 2: 4: 1, only 2: 4: 1 at or near 2: 4: a ratio of 1 would allow MOFs to form, otherwise the product would not form.
Further, the vulcanizing agent is selected from any one of thioacetamide and thiourea.
Further, the vulcanization reaction temperature is 160-180 ℃, and preferably 160 ℃.
Further, the mass ratio of the Cd/Co-MOF to the vulcanizing agent is 1: (20 to 30), preferably 1: 22.
the invention also provides the application of the Z-type heterojunction photocatalystWith, i.e. using, the Z-type heterojunction photocatalyst for catalytically decomposing water to produce H2Meanwhile, the benzaldehyde is catalyzed and oxidized to generate the benzaldehyde, and the technical scheme is as follows:
a method for producing hydrogen and benzaldehyde by photocatalysis simultaneously comprises the following steps: h is to be2Mixing O and benzyl alcohol, adding the Z-type heterojunction photocatalyst, and performing catalytic reaction under inert atmosphere and illumination to generate H2And benzaldehyde.
Further, said H2The dosage ratio of the O, benzyl alcohol and the Z-type heterojunction photocatalyst is (1-10) mL: (10-20) μ L: 1mg, preferably 5 mL: 18 μ L: 1 mg.
Further, the catalytic reaction temperature is 20-25 ℃, and preferably 25 ℃.
Further, the inert atmosphere is selected from an argon atmosphere or a nitrogen atmosphere.
Further, the illumination condition can be visible light with the wavelength of 400-780 nm, for example, the light intensity is 100mW/cm2And an LED lamp with the light wavelength of 450nm or an Xe lamp with the light wavelength of more than 400 nm.
Compared with the prior art, the invention uses Cd as the metal center2+And Co2+Sulfurizing the polymetallic MOF to obtain Cd2+And Co2+Form Co separately9S8And CdS, Co9S8And CdS forms a Z-type heterojunction inside the MOF. The present inventors determined Co by the Tauc plot method9S8And CdS with band gaps of 0.93eV and 2.46eV, respectively, and then obtaining Co through a Mott-Schottky test9S8And the conduction bands of CdS are-0.74V and-0.37V (vs. RHE), respectively. Co9S8The conduction band potential of (a) is sufficiently negative to drive a visible light driven hydrogen production reaction. Under visible light irradiation, electrons in the conduction band of CdS are preferentially transferred to Co9S8Leaving a hole, Co, in the CdS valence band9S8Photo-generated electrons on the valence band to reduce water to H2. Meanwhile, the photo-generated holes on the CdS valence band can oxidize benzyl alcohol into benzaldehyde. In addition, the electrons and Co present in the CdS conduction band9S8Light generation in VBHole bonding, indicating Co9S8The charge transfer behavior in a/CdS heterojunction is Z-type.
Therefore, the invention has the following beneficial effects:
(1) can simultaneously catalyze the reduction of water into H2Catalyzing and oxidizing the benzyl alcohol into benzaldehyde;
(2) the catalyst needs no sacrificial agent and can utilize light energy fully and effectively.
Drawings
FIG. 1 shows Co9S8A high-resolution transmission electron microscope image of the/CdS Z-type heterojunction photocatalyst;
FIG. 2 shows Co9S8Powder X-ray diffraction pattern of CdS Z-type heterojunction photocatalyst;
FIG. 3 is Co9S8H of/CdS Z-type heterojunction photocatalyst under different illumination conditions2Yield.
Detailed Description
The technical scheme of the invention is further explained by combining the specific embodiment and the attached drawings.
Example 1
This example provides a Z-type heterojunction photocatalyst prepared by a method comprising:
(1) adding Cd into the solution2+、Co2+And mixing the mixture with an organic ligand, and carrying out hydrothermal reaction to obtain Cd/Co-MOF.
Specifically, 119mg (0.39mmol) of Cd (NO)3)2·4H2O、220mg(0.76mmol)Co(NO3)2·6H2O and 56mg (0.19mmol) of 5- (5-carboxy-3-pyridinyl) -1, 3-benzenedicarboxylic acid (H)3L) was dissolved in a mixed solvent of DMF and water, and 1.25mL of glacial acetic acid was added thereto. The mixture is then transferred to an autoclave with a polytetrafluoroethylene liner at 130℃Heating in an oven for 72h for hydrothermal reaction. After the reaction was completed, it was naturally cooled to room temperature, and the obtained product was collected by centrifugation and washed several times with distilled water and ethanol. And finally drying the obtained crystal at 60 ℃ for 12h to obtain the Co/Cd-MOF.
(2) And mixing the Cd/Co-MOF with a vulcanizing agent, and carrying out a vulcanization reaction to obtain the Z-type heterojunction photocatalyst.
Specifically, 9.7mg of Co/Cd-MOF was added to a 5mL ethanol solution containing 220mg Thioacetamide (TAA). After stirring for 2min and mixing, the mixture was transferred to a 15mL autoclave with a Teflon liner and held in an oven at 160 ℃ for 24h for the vulcanization reaction. After the reaction is finished, naturally cooling to room temperature, washing the obtained precipitate for 3 times by using ethanol, and drying in an oven at 60 ℃ to obtain Co9S8a/CdSZ type heterojunction photocatalyst.
To Co9S8The structure of the/CdS Z-type heterojunction photocatalyst is characterized, and the result is as follows:
(1) morphology of
Co9S8The high resolution transmission electron microscope image of the/CdS Z-type heterojunction photocatalyst is shown in figure 1, and as can be seen from figure 1, Co9S8The particle size of the/CdS Z-type heterojunction catalyst is 10-20 nm, and the lattice spacing of 0.316nm and 0.286nm respectively corresponds to the (101) crystal face of CdS and the Co crystal face of the CdS9S8The (222) crystal plane of (c). It is clear that CdS and Co9S8The nanoparticles are tightly connected to each other and form close contacts during the migration of different metal cations in solid solution, which may facilitate the transfer of photogenerated carriers during the photocatalytic reaction.
(2) Powder X-ray diffraction
Co9S8The powder X-ray diffraction pattern of the/CdS Z-type heterojunction photocatalyst is shown in FIG. 2, and as can be seen from FIG. 2, Co9S8The powder X-ray diffraction pattern of/CdS shows two sets of characteristic peaks, which can be respectively attributed to CdS (JCPDS card41-1049) and Co9S8(JCPDS card 86-2273)。
Example 2
This example provides a method for producing hydrogen and benzaldehyde by photocatalysis, which uses the Z-type heterojunction photocatalyst for producing H by catalytic decomposition of water2Meanwhile, the method for catalyzing the benzaldehyde to be oxidized to generate the benzaldehyde comprises the following steps:
mixing 1mg of Co9S8A CdS Z-type heterojunction photocatalyst, 5mLH2O and 18. mu.L of benzyl alcohol were added to a 16mL quartz vial with a benzyl alcohol concentration of 32 mM. After sealing, the mixture was bubbled with argon for 20min, then at 450nm LED lamp (100 mW/cm)2And (2) irradiating at 25 ℃ or under a 300W Xe lamp (lambda is more than or equal to 400nm) to perform catalytic reaction for 6 h.
During the reaction, a gas chromatograph (GC-2014) is used for releasing H2Quantitative measurements were performed while using high performance liquid chromatography (LC-2030) and a nuclear magnetic resonance spectrometer (AVANCE III HD 400MHz) to quantitatively measure the benzaldehyde produced during the photocatalytic process.
FIG. 3 shows the signal H under different visible light driving2Yield of
As can be seen from FIG. 3, H is not generated in the absence of light2(ii) a The same benzyl alcohol concentration (32 mM), under Xe lamp (. lamda. gtoreq.400 nm) irradiation, H2The yield is 25900 mu mol g under the irradiation of an LED lamp-1Increased to 41200. mu. mol. g-1Indicating light absorption at H2Plays an important role in the process.
When the benzyl alcohol concentration was increased from 32mM to 160mM, H was present within 6H2The yield can reach 61924 mu mol g-1。
After 6 hours of reaction, the reaction was terminated and Co was added9S8Separating the/CdS Z-type heterojunction photocatalyst from the reaction mixture, washing and drying the reaction mixture, performing the next round of the same catalytic reaction, circulating the reaction for multiple times, wherein the reaction time is 6h each time, and performing Co circulation for four times9S8The catalytic activity of the/CdS Z-type heterojunction photocatalyst is basically kept unchanged, which shows that Co9S8the/CdS Z-type heterojunction photocatalyst has better stability.
In addition, in order to confirm the action of photogenerated holes, the photocatalytic liquid product was further analyzed by high performance liquid chromatography and nuclear magnetic resonance spectroscopy. The product benzaldehyde is detected to have high selectivity (>99.9 percent) and the conversion rate can reach 72 percent in 20 hours
Comparative example 1
Mixing 1mg of Co9S8A CdS Z-type heterojunction photocatalyst and 5mLH2O and add to a 16mL quartz vial. After sealing, the mixture was bubbled with argon for 20min, then at 450nm LED lamp (100 mW/cm)2And (2) irradiating at 25 ℃ or under a 300W Xe lamp (lambda is more than or equal to 400nm) to perform catalytic reaction for 6 h. Detection of the gaseous product by gas phase, no H detected2Is generated.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a Z-type heterojunction photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) adding Cd into the solution2+、Co2+Mixing the obtained product with an organic ligand, and carrying out hydrothermal reaction to obtain Cd/Co-MOF;
(2) and mixing the Cd/Co-MOF with a vulcanizing agent, and carrying out a vulcanization reaction to obtain the Z-type heterojunction photocatalyst.
2. The method of claim 1, wherein: the hydrothermal reaction temperature is 120-140 ℃.
3. The method of claim 1, wherein: the organic ligand is selected from 5- (5-carboxyl-3-pyridyl) -1, 3-phthalic acid.
4. The production method according to claim 3, characterized in that: the Cd2+、Co2+And organic ligand in a molar ratio of 2: 4: (1-2).
5. The method of claim 1, wherein: the vulcanizing agent is selected from thioacetamide or thiourea.
6. The method of claim 1, wherein: the vulcanization reaction temperature is 160-180 ℃.
7. The method of claim 1, wherein: the mass ratio of the Cd/Co-MOF to the vulcanizing agent is 1: (20-30).
8. A Z-type heterojunction photocatalyst is characterized in that: the preparation method of any one of claims 1 to 7.
9. A method for producing hydrogen and benzaldehyde by photocatalysis simultaneously is characterized by comprising the following steps: h is to be2Mixing O and benzyl alcohol, adding the Z-type heterojunction photocatalyst of any one of claims 1 to 7, and carrying out catalytic reaction under inert atmosphere and illumination to generate H2And benzaldehyde.
10. The method for producing hydrogen and benzaldehyde by simultaneous photocatalysis according to claim 9, wherein: said H2The dosage ratio of the O, benzyl alcohol and the Z-type heterojunction photocatalyst is (5-10) mL: (10-20) μ L: 1 mg.
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